Water-soluble reactive mono- and di-azo dyes

ABSTRACT

The present invention relates to dyes of the general formula (I) 
                         
where
     X 1  is a radical —CH 2 CH 2 Z or —CH═CH 2 , Z being analkali-eliminable group,   X 2  is alkyl, alkoxy, halogen, COOM or SO 3 M,   X 3  is a heterocyclic reactive group of the general formula (IIa) or (IIb)   
     
       
         
         
             
             
         
       
         
          or a reactive group of the formula (IIc), (IId) or (IIe) 
       
    
                         
the stated variables being as defined in claim  1,  to processes for preparing them and to their use for dyeing and printing hydroxyl-containing and/or carboxamido-containing material.

The present invention is situated within the field of fiber-reactivedyes. EP-A 785 237 discloses reactive dyes comprising the structuralelement

The present invention now provides dyes of the general formula (I)

where

-   m is 1 or 2,-   n is 0 or 1-   q is 0, 1, 2 or 3 and-   p is 0, 1 or 2,-   r is 0, 1 or 2, and-   p+r is 1 or 2 and-   X₁ is a radical —CH₂CH₂Z or —CH═CH₂, Z being an alkali-eliminable    group,-   M is hydrogen, ammonium, an alkali metal or the equivalent of an    alkaline earth metal,-   X₂ is alkyl, alkoxy, halogen, COOM or SO₃M,-   L is a direct bond or alkylene,-   L′ is a direct bond or a group of the formula

-   X₃ is a heterocyclic reactive group of the general formula (IIa) or    (IIb)

-    or a reactive group of the formula (IIc), (IId) or (IIe)

where

-   X₄ to X₆ independently are hydrogen or halogen, with the proviso    that at least one radical X₄ to X₆ is halogen,-   X₇ is halogen or X₈, and-   X₈ is a substituent of the general formula (III)

where

-   R₁ is hydrogen, alkyl or aryl,-   B is alkylene, oxygen-interrupted alkylene, arylene or arylalkylene,    and-   R₂ is a radical SO₃M, SO₂—CH₂CH₂Z or SO₂—CH═CH₂, in which Z is as    defined above-   and the ring labeled A is either absent or present.

In the compound of the general formula (I) an alkali metal M can be inparticular lithium, sodium or potassium, while calcium is a particularlysuitable alkaline earth metal. Preferably M is hydrogen or sodium.

Halogen X₂, X₄ to X₆, and X₇ is in particular fluorine or chlorine.

Alkyl R₁ or X₂ is preferably C₁–C₈ alkyl and more preferably C₁–C₄alkyl. Examples of such alkyl groups are methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Especiallypreferred alkyl groups are methyl and ethyl. Similar comments apply toalkoxy R₁ or X₂. Especially preferred alkoxy groups, therefore, aremethoxy and ethoxy.

Aryl R₁ is in particular phenyl, which may also be substituted one ormore times by, for example, C₁–C₄ alkyl, C₁–C₄ alkoxy, chloro, fluoro orthe SO₃H group. Alkylene B or L is preferably C₁–C₈ alkylene and morepreferably C₁–C₄ alkylene. Examples of such alkylene groups aremethylene, ethylene, n-propylene, isopropylene, and butylene.Oxygen-interrupted alkylene is in particular—(CH₂)_(u)—O—(CH₂)_(v)—, inwhich u and v independently are numbers from 1 to 3.

Arylene B is in particular phenylene and naphthylene, preference beinggiven to meta- and para-phenylene.

Arylalkylene B is preferably a group of the general formula (IVa) or(IVb)

where s is a number from 1 to 4 and the free bond on the aromaticnucleus may be attached either to N or to R₂.

Alkali-eliminable radicals Z, i.e., radicals Z which can be eliminatedunder dyeing conditions, include for example chloro, bromo, sulfato,thiosulfato, phosphato, C₂–C₅ alkanoyloxy such as acetyloxy, forexample, benzoyloxy, sulfobenzoyloxy or p-tolylsulfonyloxy, preferencebeing given to sulfato.

The groups, “sulfato”, “thiosulfato” and “phosphato” include both theacid form and the salt form. Accordingly, thiosulfato groups have thegeneral formula —S—SO₃M, phosphato groups the general formula —OPO₃M₂and sulfato groups have the general formula —OSO₃M, in which M is asdefined above.

Preferred compounds of the general formula (I) meet the condition p+r=1,while paricularly preferred compounds of the general formula (I) meetthe condition p+r=2. If m=1 then preferably p+r=1.

-   X₂ is preferably C₁–C₄ alkyl, C₁–C₄ alkoxy or SO₃M and more    preferably methyl, ethyl, methoxy, ethoxy or SO₃M, in which M is    hydrogen or sodium.-   L and L′ are preferably each a direct bond.-   X₃ is preferably a group of the formula

where

-   Hal′ is chloro or bromo,-   R₁′ is hydrogen, methyl, ethyl or phenyl,-   B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and-   R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.

If r is 2 then the radicals X₃ may have identical or different meanings.Similarly, the radicals X₂ may have identical or different meanings if qis 2 or 3 and the radicals X₁ may have identical or different meaningsif p is 2.

Particularly preferred dyes of the general formula (I) correspond to thegeneral formula (Ia)

where X₁ to X₃, A, L, L′, M, m, r, p and q are as defined above.

Particularly preferred dyes of the general formula (I) correspond,moreover, to the general formula (Ib)

where X₁ to X₃, A, L, L′, M, r, p and q are as defined above.

Particularly preferred dyes of the general formula (I) correspond,furthermore, to the general formula (Ic)

where M, X₂ and q are as defined above and V is X₃—NH-L- or X₁—O₂S-L′-,where X₁, X₃, A, L and L′ are as defined above.

Especially preferred dyes of the general formula (I) correspond to thefollowing general formulae (Id) to (Iq)

where in each case

-   M is hydrogen or sodium and-   X₂′ is hydrogen, methyl, ethyl, methoxy, ethoxy, COOM or SO₃M and-   U is —SO₂CH₂CH₂OSO₃M, —SO₂CH═CH₂ or —NH-U′, in which M is hydrogen    or sodium and U′ is one of the formulae

where

-   Hal′ is chloro or fluoro,-   R₁′ is hydrogen, methyl, ethyl or phenyl,-   B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and-   R₂′ is —SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.

The dyes of the general formula (I) according to the invention aregenerally in the form of preparations in solid or liquid (dissolved)form. In solid form they generally include the electrolyte salts whichare customary for water-soluble and especially fiber-reactive dyes, suchas sodium chloride, potassium chloride and sodium sulfate, and mayfurther include the assistants customary in commercial dyes, such asbuffer substances with the capacity to set a pH in aqueous solution ofbetween 3 and 7, such as sodium acetate, sodium borate, sodium hydrogencarbonate, sodium dihydrogen phosphate, sodium tricitrate, and disodiumhydrogen phosphate, small amounts of siccatives or, if they are inliquid, aqueous solution (including the thickener content customary inthe case of printing pastes), substances which ensure the durability ofsaid preparations, such as mold preventatives, for example. The dyes ofthe general formula (I) according to the invention are preferably in theform of dye powders or dye granules containing from 10 to 80% by weight,based on the powder or granules, of an electrolyte salt, also referredto as a standardizer. Granules have grain sizes in particular of from 50to 500 μm. These solid preparations may further comprise theabovementioned buffer substances in a total amount of up to 10% byweight, based on the preparation. Where the dyes are in aqueoussolution, the total dye content of such aqueous solutions is up to about50% by weight, such as between 5 and 50% by weight, for example, withthe electrolyte salt content of these aqueous solutions being preferablybelow 10% by weight, based on the aqueous solution. The aqueoussolutions (liquid preparations) may comprise the abovementioned buffersubstances, in general, in an amount of up to 10% by weight, preferablyup to 2% by weight.

Dyes of the general formula (I) where p≠0 and/or those containing agroup of the formula (IIb) in which X₈ is a group of the formula (III),while having the same chromophore, may possess a different structure inrespect of the fiber-reactive group SO₂X₁ and/or R₂. In particular, withthe same chromophore, SO₂X₁ and R₂ may on the one hand be —SO₂CH═CH₂ andon the other —SO₂CH₂CH₂Z, with particular preferenceβ-sulfatoethylsulfonyl. The fraction of the dye in vinylsulfonyl formmay be up to about 30 mol %, based on the respective dye chromophore.The molar ratio between the vinylsulfonyl dye fraction and theβ-ethyl-substituted dye fraction is preferably between 5:95 and 30:70.

The dyes of the general formula I according to the invention may beprepared, for example, by diazotizing an aromatic amine of the generalformula (V)

where p, q, r, A, L, X₁, X₂ and X₃ are as defined above and coupling thediazonium compound with a compound of the general formula (VI)

Using one equivalent of compound of the general formula (V) in thispreparation process per equivalent of compound of the general formula(VI) produces dyes of the general formula (I) according to the inventionin which m is 1. Alternatively, using two equivalents of compound of thegeneral formula (V) per equivalent of compound of the general formula(VI) produces dyes of the general formula (I) according to the inventionin which m is 2.

Where the intention is to prepare a compound of the general formula (I)according to the invention in which m is 2, the condition p+r=1 or 2 isnot met in the aromatic compounds of the general formula (V). Instead, pand r are to be chosen such that the resulting compound of the generalformula (I) according to the invention meets the condition p+r=1 or 2.

In one preferred embodiment of the preparation process according to theinvention first one equivalent of aromatic amine of the general formula(V) is diazotized and the diazonium compound is coupled with oneequivalent of a compound of the general formula (VIa)

where M is as defined above in the pH range between 0 and 6, preferablybetween 1 and 4. The resultant monoazo dyes correspond to the generalformula (Ir)

where p, q, r, A, L, X₁, X₂, X₃ and M are as defined above.

The dyes of the general formula (Ir) dye cotton in golden yellow toreddish yellow shades with good all-round fastness properties.

The dyes of the general formula (Ir) can then if desired be reacted witha second equivalent of the aromatic amine of the general formula (V),diazotized beforehand by known methods, to give disazo dyes of thegeneral formula (Ia) or (Ib).

In the preparation according to the invention of compounds of thegeneral formula (I) in which m is 2 the two equivalents of aromaticamine may be the same or different in respect of the variables p, q, r,L, L′, X₁, X₂ and X₃.

If the two equivalents of aromatic amine are the same in respect of thevariables p, q, r, L, L′, X₁, X₂ and X₃ then it is particularlypreferred to perform the reaction in a one-pot process (“one-potcoupling”). In this case two equivalents of the aromatic amine of thegeneral formula (V) are diazotized and the diazonium compound is coupledwith one equivalent of the compound of the general formula (VI).

The compounds of the general formula (I) according to the invention thatare obtained by one-pot coupling are identical with the compoundsobtained by “serial coupling”: that is, by twofold successive coupledattachment of in each case one equivalent of aromatic amine of thegeneral formula (V) of the same chemical structure.

Dyes of the general formula (I) according to the invention in which m is2 and p+r=1 may be prepared by diazotizing an aromatic amine of thegeneral formula (V) in which p+r=0 and reacting the diazonium compoundwith a compound of the general formula (VI) to give a compound of thegeneral formula (VII)

where q, n, A, X₂ and M are as defined above. Then, in a second step, anaromatic amine of the general formula (V) in which p+r=1 is diazotizedand the diazonium compound is coupled further with the compound of thegeneral formula (VII) to give the disazo dye according to the invention.

Conversely it is also possible, of course, first to diazotize anaromatic amine of the general formula (V) in which p+r=1 and to couplethe diazonium compound with a compound of the general formula (VI) togive dyes of the general formula (Is) according to the invention

where n, p, q, r, A, L, X₁, X₂, X₃ and M are as defined above and inwhich p+r=1. Then, in the second step, an aromatic amine of the generalformula (V) in which p+r=0 is diazotized and the diazonium compound issubjected to further coupling to give the disazo dye according to theinvention. In both cases monofunctional disazo reactive dyes areobtained which, given an appropriate choice of first and second diazocomponent, are isomeric with one another.

Preferred aromatic amines of the general formula (V) in which p+r=0 areaniline derivatives or naphthylamine derivatives, but especially theirsulfonic acids.

Examples that may be mentioned include aniline-2-sulfonic acid,aniline-3-sulfonic acid, aniline-4-sulfonic acid,4-methylaniline-2-sulfonic acid, 4-methylaniline-3-sulfonic acid,4-methylaniline-2,5-disulfonic acid, 4-methoxyaniline-2-sulfonic acid,4-methoxyaniline-2,5-disulfonic acid, 2-chloroaniline-5-sulfonic acid,2-chloroaniline-4-sulfonic acid, 2-methoxy-5-methylaniline-4-sulfonicacid, 2,5-dimethoxyaniline-4-sulfonic acid, aniline-2,4-disulfonic acid,aniline-2,5-disulfonic acid, 2-methoxyaniline-5-sulfonic acid,1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-3-sulfonic acid,1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid,1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid,1-aminonaphthalene-8-sulfonic acid, 1-aminonaphthalene-3,6-disulfonicacid, 1-aminonaphthalene-3,7-disulfonic acid,1-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-1-sulfonicacid, 2-aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonicacid, 2-aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-8-sulfonicacid, 2-aminonaphthalene-1,5-disulfonic acid,2-aminonaphthalene-4,8-disulfonic acid,2-aminonaphthalene-5,7-disulfonic acid,2-aminonaphthalene-6,8-disulfonic acid,2-aminonaphthalene-3,6-disulfonic acid,2-aminonaphthalene-1,5,7-trisulfonic acid and2-aminonaphthalene-3,6,8-trisulfonic acid.

Preferred aromatic amines of the general formula (V) in which p+r≠0correspond to the aforementioned compounds but additionally carry thecorresponding number of substituents -L′—SO₂X₁ and/or -L—NH—H₃.

The diazotization and coupling reactions needed to prepare the dyes ofthe general formula (I) are known per se to the skilled worker and canbe performed in conventional manner as described thoroughly in therelevant literature. In the case of the preparation processes-indicatedthe dyes of the general formula (I) according to the invention areobtained as solutions or suspensions and can be isolated by salting out,for example. The dyes can also be spray dried, although evaporativeconcentration of the solution or suspension is a further possibility.

The aromatic amines of the general formula (V) are known per se and canbe prepared by methods familiar to the skilled worker.

The compounds of the general formula (VI) have in some instanceslikewise been described (for example,3-sulfomethylaminoaniline-6-sulfonic acid in JP 60 243157 and JP 6157650). They may be prepared, for example, by reacting compounds of thegeneral formula (VIII)

in which n is 0 or 1 with formaldehyde bisulfite of the formula (IX)

where M is as defined above. For this reaction it is customary to addformaldehyde bisulfite to a solution of compound of the general formula(VIII) at a pH of from 3 to 9 and to carry out condensation at areaction temperature of from 30 to 80° C.

The reactive dyes of the general formula (I) according to the inventionpossess useful application properties. They are used for dying andprinting hydroxyl—and/or carboxamido-containing materials, in the formfor example of sheetlike structures, such as paper and leather, or offilms, of polyamide, for example, or in bulk, as for example polyamideand polyurethane, but especially in the form of fibers of the materialsmentioned. Preferably they are used for dyeing and printing cellulosicfiber materials of any kind. They are additionally suitable for dyeingor printing hydroxyl-containing fibers present in blend fabrics; forexample, blends of cotton with polyester fibers or polyamide fibers. Itis also possible to use them to print textiles or paper by the inkjetprocess.

The present invention accordingly also provides for the use of thereactive dyes of the general formula (I) according to the invention fordyeing or printing the materials mentioned and, respectively, providesmethods of dyeing or printing such materials in a conventional mannerusing as colorants one or more reactive dyes of the general formula (I)according to the invention.

Advantageously the as-synthesized solutions of the reactives dyes of thegeneral formula (I) according to the invention may be used directly as aliquid preparation for dyeing, where appropriate following addition of abuffer substance and similarly where appropriate following concentrationor dilution.

The materials mentioned are used preferably in the form of fibermaterials, particularly in the form of textile fibers, such as wovens oryarns, as in the form of hanks or wound packages.

-   Hydroxyl-containing materials are those of natural or synthetic    origin, examples being cellulose fiber materials or regenerated    products thereof and polyvinyl alcohols. Cellulose fiber materials    are preferably cotton but also include other plant fibers, such as    linen, hemp, jute, and ramie fibers. Regenerated cellulose fibers    are, for example, staple viscose and filament viscose.

Carboxamido-containing materials are, for example, synthetic and naturalpolyamides and polyurethanes, particularly in fiber form, examples beingwool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.

The reactive dyes of the general formula (I) according to the inventionmay be applied to and fixed on the substrates mentioned, particularlythe fiber materials mentioned, by the application techniques that areknown for water-soluble dyes and in particular by the techniques knownfor fiber-reactive dyes.

For instance, when applied by exhaust dyeing processes to cellulosefibers from a long liquor using any of a wide variety of acid-bindingagents with or without neutral salts, such as sodium chloride or sodiumsulfate, they produce dyeings with very good color yields. Dyeing isperformed preferably in an aqueous bath at temperatures between 40 and105° C., where appropriate at a temperature up to 130° C. underpressure, and where appropriate in the presence of customary dyeingassistants. One possible procedure in this context is to introduce thematerial into the warm bath and to heat the bath gradually to thedesired dyeing temperature, and to complete the dyeing operation at thattemperature. The neutral salts which hasten the exhaustion of the dyesmay also, where appropriate, not be added to the bath until the actualdyeing temperature has been reached.

The padding process likewise provides excellent color yields and verygood color build on cellulose fibers, in which case fixing can beaccomplished conventionally by batching at room temperature or elevatedtemperature, at up to about 60° C., for example, by steaming or usingdry heat.

Similarly, the customary printing processes for cellulose fibers, whichcan be carried out either in one phase, by printing for example with aprint paste comprising sodium bicarbonate or another acid-binding agentand by subsequent steaming at 100 to 103° C., or in two phases, by forexample printing with a neutral or weakly acidic print color and bysubsequent fixation either by passing the printed material through a hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquor with subsequent batching orsteaming or dry heat treatment of the alkali-overpadded material,produce strong prints having well-defined contours and a clear whiteground. The outcome of the prints is largely independent of variationsin the fixing conditions.

When fixing by means of dry heat in accordance with the customarythermofix processes use is made of hot air and from 120 to 200° C.Besides the customary steam at 101 to 103° C. it is also possible to usesuperheated steam and pressurized steam at temperatures of up to 160° C.

The acid-binding agents which bring about the fixation of the dyes onthe cellulose fibers include for example water-soluble basic salts ofthe alkali metals and likewise alkaline earth metals of organic orinorganic acids or compounds which release alkali in the heat. Mentionmay be made in particular of the alkali metal hydroxides and alkalimetal salts of weak to medium-strength organic or inorganic acids, thepreferred alkali metal compounds being the sodium and potassiumcompounds. Examples of such acid-binding agents include sodiumhydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate,potassium carbonate, sodium formate, sodium dihydrogenphosphate,disodium hydrogenphosphate, sodium trichloroacetate, waterglass ortrisodiumphosphate. The reactive dyes of the general formula (I)according to the invention are notable for high reactivity, goodfixability, very good build, and a high level of fastness to light andto light coupled with perspiration. They can therefore be used inaccordance with the exhaust dyeing process at low dyeing temperaturesand require only short steaming times in pad-steam processes. Thedegrees of fixation are high, and the unfixed portions are easily washedoff, the difference between the degree of exhaustion and the degree offixation being remarkably small—that is, the soaping losses being verysmall. They are also particularly suitable for printing, especially oncotton, but also for printing nitrogenous fibers, such as wool or silkor blend fabrics containing wool or silk.

The reactive dyes of the general formula (I) according to the inventionhave the further feature that, following the dyeing operation, unfixeddye portions on the fiber material are very easily washed off withoutwhites in the same wash being stained by the dye that becomes detached.This brings advantages of the dyeing operation by saving on wash cyclesand hence on costs.

The dyeings and prints produced with the reactive dyes of the generalformula (I) according to the invention, especially on cellulose fibermaterials, possess high color strength and a high fiber-dye bondstability both in the acidic and in the alkaline range, as well as goodlight fastness and very good wet fastness properties, such as wash,water, seawater, cross-dyeing, and perspiration fastnesses, and alsogood fastness to dry heat setting, pleating, and crocking.

The examples below serve to illustrate the invention. The parts andpercentages are by weight unless noted otherwise. Parts by weight relateto parts by volume as the kilogram relates to the liter.

-   The compounds described by formula in the examples are given in the    form of the free acid. Generally, however, they are prepared and    isolated in the form of their alkali metal salts, such as lithium,    sodium or potassium salts, and are used in the form of their salts    for dyeing. Similarly, the starting compounds and components    specified in free acid form in the following examples, especially    tabular examples, can be used in the synthesis as such or in the    form of their salts, preferably alkali metal salts.

The absorption maxima (λ_(max)) in the visible range reported for thedyes according to the invention were measured on aqueous solutions oftheir alkali metal salts.

EXAMPLE 1

Synthesis of a Compound of the Formula (VI) (Precursor)

18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 partsof water and converted to a neutral solution by adding 20% strengthsodium hydroxide solution. At 20° C., 14.7 g of formaldehyde bisulfite(Na salt) are added and the mixture is heated to 50° C. It issubsequently stirred for 4 hours at a pH from 5.0 to 5.5. The solutionobtained is concentrated by evaporation or reacted further directly.

The yellowish residue obtained following evaporative concentrationcorresponds to the compound of the formula (VIa)

¹H-NMR (400 MHz, d₆-DMSO): δ (ppm)=3.77 (d, 2 H, ³J=6.6 Hz, CH₂), 5.28(s, 2 H, NH₂), 5.54 (t, 1 H, ³J=6.6 Hz, NH), 5.82 (dd, 1 H, ³J=8.1 Hz,⁴J=2.2 Hz, H_(ar)), 5.86 (d, 1 H, ⁴J=2.2 Hz, H_(ar)), 7.08 (d, 1 H,³J=8.1 Hz, H_(ar)).

EXAMPLE 2

A suspension of 28.1 g of 4-(2′-sulfatoethylsulfonyl)aniline in 200parts of water is admixed at 15° C. in succession with 0.5 g of acommercial dispersant and 21 parts of 31% strength hydrochloric acid andthe mixture is stirred for 15 minutes thereafter. Then 13.2 parts of 40%strength aqueous sodium nitrite solution are added dropwise and themixture is stirred for 60 minutes more with nitrite in excess. Excessnitrite is then destroyed by adding 10% strength amidosulfuric acid. Thesuspension of the diazonium salt is then admixed with the solution ofthe compound of the formula (Via) prepared in Example 1. The pH is thenadjusted to 5–6 by adding 15% strength sodium carbonate solution andcoupling is completed at 20° C.

Evaporative concentration of the solution gives a dye of the formula(Ie)

which dyes or prints cotton in reddish yellow shades (λ_(max)=445 nm)with good fastness properties.

The dyes of Examples (3) to (17) are obtained analogously by diazotizingamines R-NH₂ as described in Example 2 and coupling the diazoniumcompounds with the compound (VIa).

Ex. R—NH₂ Coupling component Shade λ_(max) (nm) 3)

yellow 416 4)

yellow 422 5)

yellow 406 6)

yellow 428 7)

yellow 446 8)

yellow 412 9)

yellow 409 10)

yellow 407 11)

yellow 404 12)

yellow 408 13)

yellow 405 14)

yellow 436 15)

yellow 438 16)

yellow 429 17)

yellow 430

EXAMPLE 18

18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 partsof water and converted to a neutral solution by adding lithium hydroxidesolution. This solution is cooled to 10° C. and admixed dropwise overone hour with 17.4 parts of 2,4,6-trifluoropyrimidine, a pH of 5.5 beingmaintained using 15% strength sodium carbonate solution. When theaddition is complete the mixture is warmed to 20–25° C. and stirred foran hour thereafter. It is then filtered and 6.9 parts of sodium nitriteare added.

The filtrate is cooled to 10° C. by introduction of ice and is addeddropwise over 30 minutes to 100 parts of ice and 60 parts ofconcentrated hydrochloric acid (31%). This mixture is stirred for anhour and then the excess nitrite is destroyed by adding amidosulfuricacid.

The solution of the compound (VIa) described in Example 1 is then addeddropwise to the acid diazotization, after which the pH is adjusted to5.0–5.5 by adding 15% strength sodium carbonate solution.

The solution obtained is concentrated by evaporation to give a dye ofthe formula

which dyes or prints cotton in yellow shades (λ_(max)=406 nm) with goodfastness properties.

The dyes of Examples (19) to (32) are obtained analogously bydiazotizing and subsequently coupling the amino compounds R-NH₂indicated in the table below by the method indicated in Example 18.

Ex. R—NH₂ Coupling component Shade λ_(max) (nm) 19)

yellow 417 20)

yellow 416 21)

yellow 418 22)

yellow 417 23)

yellow 421 24)

yellow 418 25)

yellow 415 26)

yellow 412 27)

yellow 415 28)

yellow 414 29)

yellow 412 30)

yellow 412 31)

yellow 415 32)

yellow 414

EXAMPLE 33

28.1 parts of 4-(2′-sulfatoethylsulfonyl)aniline are dissolved in 250parts of water by neutralization of solid sodium bicarbonate. 4.2 partsof sodium fluoride are added to the solution, which is subsequentlycooled to 0–5° C. by adding ice. Then, over the course of 5 minutes,13.5 parts of trifluorotriazine are added dropwise, the pH initiallyfalling rapidly and then leveling out at 4.5 to 5.0.

When the addition is complete, stirring is continued for 15 minutes.Subsequently, a neutralized solution of 18.8 parts of2,4-diaminobenzenesulfonic acid in water is added dropwise and the pH isadjusted to 6.0–6.5. The reaction is completed by heating at from 30 to35° C. followed by 60 minutes of stirring. The resulting solution isfiltered and 6.9 parts of sodium nitrite are added.

The solution obtained is cooled to 10° C. by introduction of ice andadded dropwise over 30 minutes to 100 parts of ice and 60 parts ofconcentrated hydrochloric acid (31%). This mixture is stirred for 1 hourand then the excess nitrite is destroyed by adding amidosulfuric acid.

The solution of the compound (Via) described in Example 1 is thenintroduced dropwise to the acid diazotization.

A pH of from 2.0 to 2.5 is established. After an hour of subsequentstirring the mixture is adjusted to a pH of 5.5 using sodium carbonatesolution and then is buffered with NaH₂PO₄/Na₂HPO₄. The resultingsolution is concentrated by evaporation.

This gives a dye of the formula

which dyes or prints cotton in yellow shades (λ_(max)=408 nm) with goodfastness properties.

The dyes of Examples (35) to (47) are obtained analogously bydiazotizing and subsequently coupling the amino compounds R-NH₂indicated in the table below by the method indicated in Example 33.

λ_(max) Ex. R—NH₂ Coupling component Shade (nm) 34)

yellow 416 35)

yellow 414 36)

yellow 419 37)

yellow 419 38)

yellow 421 39)

yellow 422 40)

yellow 422 41)

yellow 419 42)

yellow 418 43)

yellow 408 44)

yellow 409 45)

yellow 407 46)

yellow 409 47)

yellow 411

EXAMPLE 48

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250parts of water is admixed at 15° C. in succession with 0.5 g of acommercial dispersant and 25 parts of 31% strength hydrochloric acid andthe mixture is stirred for 15 minutes thereafter. Then 16 parts of 40%strength aqueous sodium nitrite solution are added dropwise and themixture is subsequently stirred for 60 minutes with the nitrite inexcess.

Excess nitrite is then destroyed by adding 10% strength amidosulfuricacid. The dye solution described in Example 2 is then added to thediazonium salt suspension, followed by stirring for 15 minutes. The pHis then adjusted to 5.0–5.5 by adding 15% strength sodium carbonatesolution, and coupling is completed.

The solution obtained is concentrated by evaporation to give a dye ofthe formula

which dyes or prints cotton in a dull orange (λ_(max)=428 nm).

The dyes of the general formula

set out in the table below are obtained by reacting the compoundprepared as in Example 1 first as described in Example 2 with an amineA₁-NH₂ and then as described in Example 48 with an amine A₂-NH₂.

Ex. A₁—NH₂ A₂—NH₂ Shade 49)

dull orange 50)

dull orange 51)

dull orange 52)

dull orange 53)

dull orange 54)

dull orange 55)

dull orange 56)

dull orange 57)

dull orange 58)

dull orange 59)

dull orange 60)

dull orange 61)

dull orange 62)

dull orange 63)

dull orange 64)

dull orange 65)

dull orange 66)

dull orange 67)

dull orange 68)

dull orange 69)

dull orange 70)

dull orange 71)

dull orange 72)

dull orange 73)

dull orange 74)

dull orange 75)

dull orange 76)

dull orange 77)

dull orange 78)

dull orange 79)

dull orange 80)

dull orange 81)

dull orange 82)

dull orange 83)

dull orange 84)

dull orange 85)

dull orange 86)

dull orange 87)

dull orange 88)

dull orange 89)

dull orange 90)

dull orange 91)

dull orange

EXAMPLE 92

17.3 parts of aniline-4-sulfonic acid are dissolved in 200 parts ofwater and acidified by adding 21 parts of 31% strength hydrochloricacid. Ice cooling to 10–15° C. is followed by dropwise addition of 13.2parts of 40% strength sodium nitrite solution. With an excess ofnitrite, stirring is conducted for 60 minutes. The excess is thenreduced by adding a few drops of 10% strength amidosulfuric acidsolution.

The solution obtained in accordance with Example 1 is then added to thediazonium salt suspension, the pH is adjusted to 4–5 by adding 15%strength sodium carbonate solution, and coupling is completed.

This gives the solution of a dye of the formula

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250parts of water is admixed at 15° C. in succession with 0.5 g of acommercial dispersant and 25 parts of 31% strength hydrochloric acid andsubsequently stirred for 15 minutes. Then 16 parts of 40% strengthaqueous sodium nitrite solution are added dropwise and the mixture issubsequently stirred for 60 minutes with an excess of nitrite.

Excess nitrite is then destroyed by adding 10% strength amidosulfuricacid. The above dye solution is then added to the diazonium saltsuspension and the mixture is stirred for 15 minutes. The pH is thenadjusted to 5.0–5.5 by adding 15% strength sodium carbonate solution,and coupling is completed.

The solution obtained is concentrated by evaporation to give a dye ofthe formula

which dyes or prints cotton in yellowish brown shades (λ_(max)=431 nm).

EXAMPLES 93 TO 135

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 92 bydiazotizing a reactive amine A₁-NH₂ in accordance with Examples 49 to 91instead of 4-(2′-sulfatoethylsulfonyl) aniline and carrying out couplingin the second stage.

EXAMPLE 136

19.1 parts of aniline-4-sulfonic acid are dissolved in 220 parts ofwater and acidified by adding 23 parts of 31% strength hydrochloricacid. Ice cooling to 10–15° C. is followed by dropwise addition of 14.5parts of 40% strength sodium nitrite solution. With an excess ofnitrite, stirring is conducted for 60 minutes. The excess is thenreduced by adding a few drops of 10% strength amidosulfuric acidsolution.

The dye solution described in Example 2 is then added to the diazoniumsalt suspension, the pH is adjusted to 4–5 by adding 15% strength sodiumcarbonate solution, and coupling is completed.

The resulting solution is dried by evaporation to give the dye offormula

which dyes or prints cotton in orange-brown shades (λ_(max)=435 nm).

EXAMPLES 137 TO 181

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 136 byusing a solution of a dye according to Examples 3 to 47 instead of thedye solution described in Example 2.

EXAMPLE 182

30.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 300parts of water and acidified by adding 21 parts of 31% strengthhydrochloric acid. Ice cooling to 10–15° C. is followed by dropwiseaddition of 13.2 parts of 40% strength sodium nitrite solution. With anexcess of nitrite, stirring is conducted for 60 minutes. The excess isthen reduced by adding a few drops of 10% strength amidosulfuric acidsolution.

The solution obtained in accordance with Example 1 is then added to thediazonium salt suspension, the pH is then adjusted to 4–5 by adding 15%strength sodium carbonate solution, and coupling is completed.

This gives the solution of a dye of the formula

A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250parts of water is admixed at 15° C. in succession with 0.5 g of acommercial dispersant and 25 parts of 31% strength hydrochloric acid andsubsequently stirred for 15 minutes. Then 16 parts of 40% strengthaqueous sodium nitrite solution are added dropwise and the mixture issubsequently stirred for 60 minutes with an excess of nitrite.

Excess nitrite is then destroyed by adding 10% strength amidosulfuricacid. The above dye solution is then added to the diazonium saltsuspension and the mixture is stirred for 15 minutes. The pH is thenadjusted to 5.0–5.5 by adding 15% strength sodium carbonate solution,and coupling is completed.

The solution obtained is concentrated by evaporation to give a dye ofthe formula

which dyes or prints cotton in yellowish brown shades (λ_(max)=439 nm).

EXAMPLES 183 TO 225

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 182 bydiazotizing a reactive amine A₁-NH₂ in accordance with Examples 49 to 91instead of 4-(2′-sulfatoethylsulfonyl)ani and carrying out coupling inthe second stage.

EXAMPLE 226

33.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 350parts of water and acidified by adding 25 parts of 31% strengthhydrochloric acid. Ice cooling to 10–15° C. is followed by dropwiseaddition of 14.5 parts of 40% strength sodium nitrite solution. With anexcess of nitrite, stirring is conducted for 60 minutes. The excess isthen reduced by adding a few drops of 10% strength amidosulfuric acidsolution.

The dye solution described in Example 2 is then added to the diazoniumsalt suspension, the pH is adjusted to 4–5 by adding 15% strength sodiumcarbonate solution, and coupling is completed.

The resulting solution is dried by evaporation to give the dye offormula

which dyes or prints cotton in yellow to orange-brown shades(λ_(max)=429 nm).

EXAMPLES 227 TO 271

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 226 byusing a solution of a dye according to Examples 3 to 47 instead of thedye solution described in Example 2.

EXAMPLE 272

A suspension of 61.8 g of 4-(2′-sulfatoethylsulfonyl)aniline in 500parts of water is admixed at 15° C. in succession with 0.5 g of acommercial dispersant and 50 parts of 31% strength hydrochloric acid andsubsequently stirred for 15 minutes. Then 32 parts of 40% strengthaqueous sodium nitrite solution are added dropwise and the mixture issubsequently stirred for 60 minutes with an excess of nitrite.

Excess nitrite is then destroyed by adding 10% strength amidosulfuricacid. The solution obtained in accordance with Example 1 is then addedto the diazonium salt suspension and the mixture is stirred for 15minutes. The pH is then adjusted to 5.0–5.5 by adding 15% strengthsodium carbonate solution, and coupling is completed.

The solution obtained is concentrated by evaporation to give a dye ofthe formula

which dyes or prints cotton in a dull orange to orange shade(λ_(max)=428 nm).

EXAMPLES 273 TO 317

Dull orange dyes of the formula

are obtained in analogy to the procedure described in Example 272 bydiazotizing 2.2 equivalents of a reactive amine A₁-NH₂ in accordancewith Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline andreacting the diazonium compound with one equivalent of the coupler fromExample 1.

1. A dye of the general formula (I)

where m is 1 or 2, n is 0 or 1, q is 0, 1, 2 or 3 and p is 0, 1 or 2, ris 0, 1 or 2, and p+r is 1 or 2 and X₁ is a radical —CH₂CH₂Z or —CH═CH₂,Z being an alkali-eliminable group, M is hydrogen, ammonium, an alkalimetal or the equivalent of an alkaline earth metal, X₂ is alkyl, alkoxy,halogen, COOM or SO₃M, L is a direct bond or alkylene, L′ is a directbond or a group of the formula

X₃ is a heterocyclic reactive group of the general formula (IIa) or(IIb)

or a reactive group of the formula (IIc), (IId) or (IIe)

where X₄ to X₆ independently are hydrogen or halogen, with the provisothat at least one radical X₄ to X₆ is halogen, X₇ is halogen or X₈, andX₈ is a substituent of the general formula (III)

where R₁ is hydrogen, alkyl or aryl, B is alkylene, oxygen-interruptedalkylene, arylene or arylalkylene, and R₂ is a radical SO₃M, SO₂-CH₂CH₂Zor SO₂-CH═CH₂, in which Z is as defined above and the ring labeled A iseither absent or present.
 2. A dye as claimed in claim 1, wherein X₂ isC₁–C₄ alkyl, C₁–C₄ alkoxy or SO₃M, M being as defined in claim
 1. 3. Adye as claimed in claim 1, wherein X₃ is a group of the formula

where Hal′ is chloro or bromo, R₁′ is hydrogen, methyl, ethyl or phenyl,B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and R₂′ is—SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.
 4. The dye as claimed in claim 1, whereinm is
 1. 5. The dye as claimed in claim 1, wherein m is
 2. 6. The dye asclaimed in claim 1, corresponding to the general formula (Ia)

where X₁ to X₃, A, L, L′, M, m, r, p and q are as defined in claim
 1. 7.The dye as claimed in claim 1, corresponding to the general formula (Ib)

where X₁ to X₃, A, L, L′, M, r, p and q are as defined in claim
 1. 8.The dye as claimed in claim 1, corresponding to the general formula (Ic)

where M, A, X₂ and q are as defined in claim 1 and V is X₃-NH-L- orX₁-O₂S-L′-, where X₁, X₃, L and L′ are as defined in claim
 1. 9. The dyeas claimed in claim 1, corresponding to one of the general formulae (Id)to (Iq)

where in each case M is hydrogen or sodium and X₂′ is hydrogen, methyl,ethyl, methoxy, ethoxy, COOM or SO₃M and U is —SO₂CH₂CH₂OSO₃M,—SO₂CH═CH₂ or —NH-U′, in which M is hydrogen or sodium and U′ is one ofthe formulae

where Hal′ is chloro or fluoro, R₁′ is hydrogen, methyl, ethyl orphenyl, B′ is ethylene, propylene or —CH₂CH₂—O—CH₂CH₂- and R₂′ is—SO₂CH₂CH₂OSO₃M or —SO₂CH═CH₂.
 10. A process for preparing a dye of thegeneral formula (I) as claimed in claim 1, which comprises diazotizingan aromatic amine of the general formula (V)

where p, q, r, L, X₁, X₂ and X₃ are as defined in claim 1 and couplingthe diazonium compound with a compound of the general formula (VI)


11. A process of dyeing of a hydroxyl- and/or carboxamido-containingmaterial which comprises contacting the material with the dye of thegeneral formula (I) as claimed in claim
 1. 12. A process of dyeing of ahydroxyl- and/or carboxamido-containing material which comprisescontacting the material with the dye of the general formula (I) asclaimed in claim
 9. 13. The process as claimed in claim 11, wherein thematerial is a fiber material.
 14. The process as claimed in claim 12,wherein the material is a fiber material.